Nitro derivative of alpha-naphthoyl-omicron-benzoic acid



Patented July 11,1933 7 ROGER F unem ynpmoi EARL "m as iom m efenem ii-KAnn r VIKTOR M; WEINMAYR, or MILWAUKEE, W sconsin,- ASSIQNOBS cro E. DU"'PONT DE NEMOURS a, WARE I a v w rrno DERIVATIVE 0F wmr goiii mj zmq cmf i i No Drawing. 7

This invention relates to novel intermediates for, dyestuffs. Moreparticularly, this invention deals Witlrnitro-derivatives ofalpha-naphthoyl-o-benzoic acid and a' fprocess ofalpha-,naphthoyl;o-benzoic acid: 111 thefirst case,-that is, undermilder conditions of.

nitration, the nitro groupyenters the 8- posi tion andrproduces-'8-nitro-5 halogen-li i d e naphthoylQ-benzoic V acid. -Und erdrastic-- conditions, for instance, ,When using larger quantities ofcnitric acid, the =-'halogen atoiniseliminated, producing 5,8-d-initro-l-naphthoyl-2-benzoicacid.

v The novel products are useful asifinter- Inediates for other organic.compounds use fulin the dyestutf art. -j p f v ltis, accordingly, anobject' of this inven tion to produce novel intermediates for dyestuffshavingthe following generalformula:

wherein stands for a nitro group or a halogen atom.

lVithout limiting our invention to any particular procedure, thefollowing examples Will serve to illustrate our preferred mode ofoperation. Parts given are parts by Weight.

97 parts of 5-bromo-1-naphthoyl-2-benzoic acid are dissolved in 550parts of 100% sulfuric acid at C. and nitrated under theory. WhenCOMPANY, or wIL INGToKmn avi/ aiin, A 'conronn'rroiv or DELA;

- mixed acidi conet acid at; 5 to 2 1092C; After stirring iforfonef hourat this temperature, a: test shows no free-nitric acid. ;The mass isdilutedzwith 2000'. part5 -.ofgiceyrwater ;'.the nitro; body is;filtered and Washed, acid free. i The yield is- 108 parts which:is1substantiallyequal :tol

v repeatedly vrecrystallized' from hot nitrobenzene, a product isobtained having-i a;lilieltillgpoint 0f 230+2329 11G. by the capillarytube method (Whenhea'tediup/ from a: cold'zbath) I I This product?analyzes llatom of bromine per molecule; 5;...1 fw- ;When' reduoedifwithiron and acid,'.this product yields, not. the'.ffree;,amine,' but'arcompound Which appearS to bea 'pyrr'olej-of the following-formula: r

ltfoildwsfthrefqre, that the IiitiatlQh panzoic acid of the followingformula z" 109 parts of 5-chlor-1'enaphthoyl-2 -benzoic acid aredissolved in 600 parts of 100% 05 C. With 110 parts of a nitratingmixture containing nitric acid and 69% sulfuric acid. The finishednitration mass is poured 'into 4000 parts of ice and water, filtered and-Washed acid free,v The yield is about 126 parts of dry product, whichis substantially equal to theory. Onrcrystallization from chlor-benzene,a, product having a melting point of 233-234;" is obtained; It is'mostsulfuric acid at 2025 G and nitrated at 7 probably8-nitro-5-chloro-Y-naphthoyl-Q- ring, 45, parts of concentrated. nitricacid.v The temperature of the reaction should pref-,-

benzoic acid.

Example 3.-,8dimitro-1-nwphthoyl2- I benzoic acid. e I p Into a solutionof parts of 5-brom0-1"- naphthoyl-2-benzoic acid; in 160 partsof aceticanhydride, are dropped in slowly, with stirerablynot' be allowed to goabove 30 C.

After the nitric acid has all been added, the

solution is stirrcdfor eight hours, during which time anappreciable,quantityof-the yellow 5,8'-dinitro-1'-naphthoy1 2-benzoicacid precipitates, which is then filtered. The

. volume of water and allowed to stand over probably acetic anhydridefiltrate is poured into a large night to decompose theacetic 'anhydride.1 A yellowv precipitate is here produced, which is filteredand added tothe preceding filter cake. The joint filter cake is then crystalliz'edtwice fromboiling toluene. If heated rapidly itmelts sharply withdecomposition at 262-263 C. Analysis shows it to be most 5 ,8-dinitro-1Cnaphthoyl-EZ-benzoicacid a i It will be understood thatmanyvariations and modifications are possible in our preferred procedurewithout departing from-the spirit of this invention. f

"In the aboveexamples the product was isolated as free acid. Byneutralization, for

instance with caustic soda, the corresponding salts, such as the-sodiumsalt, may be readily obtained. It should be understood, there fore, thatin our claims belowwe'consider the salts of our novel compounds asequivalents ofthe free acid. V

, o-ben'zoic acid l. vAjnitroderivative of alpha naphthoy'lpossessingthefollowing general formula:

res I "wherein X standsfor halogen or the nitro' group. i

2. 5',8' dinitro-1- naphthoyl 2 benzolc acid. o

' 3. 5 halogen-snitro-l -naphthoyl-2:ben-

'zoic acid. V I 4. The process of producing a nitro derivative ofalpha-naphthoyl-o-benzoic acid oithe general formula wherein X standsfor halogen or thenitro group, which comprises reacting with nitric acidupon 5-halogen-1Qnaphthoyl-2-benzoic acid. A V

5. The process of producing 5,8-dinitro- 1 -naphthoyl2+benzoicacid whichcomprises reacting with nitric acid upon 5- -halogen-ln itro- 1-naphthoyl- 2 -.benzoic acid which com: prises reacting-with nitric acidupon 5'-chlosulfuric acid. I I

' 10. The process ofproducing 5-bromo-8- nitro-1-naphthoyl-2-benzoicacid which comprises'reacting-with nitric acid upon 5 -bromo-1i-naphthoyl-2ebenzoic acid, dissolved in sulfuric acid. i

ro-l-naphthoyl-2 -benzoic acid, dissolved In testimony whereof we afiixour signatures. n

ROGER ADAMS. EARL HANFORD JOHNSON. VIKTOR M.

